Process for treating hydrocarbons containing olefins



Patented Mar. 2, 1943 PROCESS FOR TREATING HYDROCARBONS CONTAINING OLEFINS Karl Korpi, Redondo Beach, Calif., assignor to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Application March 2, 1940, Serial No. 321,983

15 Claims.

The present invention relates to a process for reducing the olefin hydrocarbon content of hydrocarbon mixtures containing the same, as for example, in the purification of aromatic hydrocarbon solvents by reducing the olefin hydrocarbon content thereof. The invention relates particularly to a process for converting naphthene hydrocarbons to aromatic hydrocarbons and also to the conversion of olefin hydrocarbons to paramnic, naphthenic and aromatic hydrocarbons. This application is a continuation, in part,of my copending application Serial No. 319,687 filed February 19, 1940.

It is known to produce aromatic hydrocarbon solvents by solvent extraction of straight run gasolines particularly those obtained from California or asphalt base crude oils which are relatively free from olefin hydrocarbons. Past attempts to produce aromatic solvents from gasolines obtained by thermal pyrolysis and/or polymerization of hydrocarbons have not been successiul principally for the reasons that (1) the v available cracked gasolines have not been particularly rich in aromatic hydrocarbons and (2) these cracked gasolines have contained large amounts of olefinic materials. The first objection has been eliminated to a large extent with the advent of catalytic cracking which will make available pressure distillates containing as much as 50% by volume of aromatic hydrocarbons. The aromatic content of these pressure distillates is about three times as high as that of straight run gasolines obtained from Western crudes and some pressure distillates produced by simple thermal means. duced by catalytically cracking oils are a particularly rich source of aromatics from which aromatic solvents may be produced.

However, the recovery of the aromatic hydrocarbons irom cracked gasoline has been somewhat uneconomical principally due to the presence of olefin hydrocarbons in the cracked gasoline. The solvent extraction of the cracked gasoline for recovery of the aromatics, as for example, with liquid sulfur dioxide, has resulted in the simultaneous extraction of both the olefin and aromatic hydrocarbons. In order to reduce the olefin content of the aromatic extract to what may be considered a satisfactory value, a rigorous and wasteful sulfuric acid treatment has been required. Straight run gasolines containing aromatics are not subjected to this disadvantage since these are relatively free from olefins.

It is an object of my invention to reduce the Thus, cracked gasolines pro- Such catalytic treatment results in converting the olefins into non-olefinic materials such as naphthenic, aromatic and paraflinic hydrocarbons so that the non-aromatic materials may be separated from the aromatic hydrocarbons by simple extraction with selective solvents such as liquid sulfur dioxide. Y

The reactions involved in the thermal catalytic treatment are numerous depending upon the character of the stock undergoing treatment and 1 on the conditions of operation. When treating stocks containing olefins, it is believed that a major reaction is in the cyclization of the olefins into cyclo-paraflin hydrocarbons or naphthenes. Another major reaction taking place resides in the formation of paraffin hydrocarbons from the olefins. Another major reaction of great importance is in the formation of aromatic hydrocarbons irom either or both the cyclo-paraflln hydrocarbons present in the original stock or,

produced from the olefin hydrocarbons. In one case, I subjected to the catalytic treatment a hydrocarbon fraction composed of about 80% olefins and 70% paraflins and obtained a resulting product composed of 5% olefins, aromatics, 12% naphthenes and 68% paraflins. This indicates that olefins were changed to cycloparafllns, paraflins and aromatics during the treatment. In another case, a hydrocarbon fraction composed of approximately 50% aromatics,

% naphthenes and 20% parafiins was treated by the catalytic process of my invention. The resulting product of the treatment was composed of approximately 80% aromatics and 20% parafflns. The increase in aromatics from toindicates that all of the naphthenes we're converted into aromatic hydrocarbons without substantially changing the paraiiins present.

It is another object of my invention to convert olefin hydrocarbons into paraflin, naphthene and aromatichydrocarbons by subjecting hydrocarbon fractions containing substantial amounts of olefins to thermal catalytic treatment.

vantage resides in the fact It is thus another object of my invention to subject naphthene hydrocarbon fractions to cat-. alytic thermal treatment to transform the naphthene hydrocarbons intoaromatic hydrocarbons.

I have further discovered that the process of soda and again drying is very important to ob-, tain a catalyst adapted to produce superior catalytic effect. I have found that when the phosdeolefination results in materially reducing the other forms of phosphoric acid such as tetra,-

meta and pyro phosphoric acid to be good catalystsp It is preferable to employ a carrier for the catalyst. Carriers which may be used include charcoal, carborundum, coke and like carbonaceous materials, alumina, clay and the like. I prefer, however, to use a substantially neutral carrier such as charco'al, carborundum, coke and graphite. Also such other neutral carriers as V preformed phosphates and other mineral acid salts of metals. The catalytic material is pref- I erably prepared by adsorbing orthophosphoric' acid or other phosphoric acids on the carrier particles of mitable size and porosity and heating the mixture to dryness ata temperature of 300- 400 F. The amount of catalyst which is ad-v sorbed on the carrier may vary within wide limits depending upon the character of the catalyst and the carrier. With the phosphoric acid catalysts, I have found it desirable to adsorb as much as to 150 ml. of the acid of 75-85% H3P4 concentration on 250 ml. of the granular carrier. I have found that by saturating the carrier with catalyst and then drying the saturated carrier that the catalytic life of the catalyst is greatly increased over that obtained by adsorbing smaller quantities of the catalyst. The strength of the catalyst employed should not preferably be less-thansubstantially 50% lIsPCM.

Using the above catalyst in treating pressure distillates containing about 20% olefins, I have obtained a reduction of 50-60% in olefin content per pass of the pressure distillate vapors over the catalyst while maintaining a temperature of 750-800 F. and atmospheric pressure in the re-' actor containing the catalyst.

A catalyst which I have found to be superior to straight phosphoric acid is one in which the phosphoric acid is partially or totally neutralized by means of a caustic alkali, (potassium, lithium and sodium hydroxides). Such a catalyst maybe prepared by first adsorbing the phosphoricacid on the carrier such as charcoal and drying the mixture when necessary by gentle heating. The phosphoric acid on the carrier is then partially or totally neutralized by adding thereto a caustic solution of alkali. The resulting mixture is again dried, heating to a temperature of 300-400 F. when necessary to obtain the drying. One advantage in using a phosphoric acid catalyst which has been partially or totally neutralized with alkali is the fact that this catalyst doesnot volatilize as readily as straight phosphoric acid, thus enabling the catalyst to be used for a considerably longer period of time. Another adthat this catalyst is less corrosive to the reactor and accessory equipment than the straight phosphoric acid would be.

The above procedure of first adsorbing the catalyst on the carrier. drying, adding the caustic phoric acid is first partially or totally neutralized before being adsorbed on the carrier and dried that the resulting catalyst has only a moderate effect in the catalytic process.

Using this catalyst for treating pressure distillate vapors containing 20% olefins, I have ob-' tained a reduction of 70-90% in olefin content in a single pass of the material over the catalyst while maintaining a temperatureof 750-300 F.

and atmospheric pressure in the reactor. Further reduction in olefincontent may be obtained by decreasing the rate of introduction of hydrocarbon to the reactor or by recycling the product of the first passage through the reactor.

In producing the partially neutralized catalyst, I have discovered that the best results are obtained when the phosphoric acid is neutralized with less than one equivalent of the caustic alkali per mol of the acid. I have found the preferred neutralization to be within the range of V6 to equivalents per mol of acid. For example, I have obtained olefin reduction to the extent of nearly 90% in a single pass of the olefinic stock through a phosphoric acid catalyst which hadbeen neutralized with M; to equivalents of caustic alkali per mol of the acid. Using straight phosphoric acid catalyst, the reduction in olefin content was about per pass through the catalyst and using phosphoric acid catalyst which had been partially neutralized with equivalents of the alkali per mol of the acid, the reduction in olefin content of the stock was about 77% per p s.

Using phosphoric acid catalysts which had been.

partially neutralized with one, one and one-half and two equivalents of the caustic alkali per mol of the acid,the catalysts were eflective in reducing the olefin contents of stock by approximately 72%,

% and 56% A completely neunon-olefin hydrocarbons and preferably to use a v phosphoric acid catalyst which has been neutralized with approximately Y; to equivalents of caustic alkali per mol of the acid.

I have found that the presence ofmoisture during the reaction aids materially in prolonging the catalytic activity of the catalyst used in the process of treating hydrocarbons particularly when using catalyst ofthe phosphoric acid type. I have observed that the presence of moisture in the reactor has prolonged the life of the catalyst more than 40 hours without materially decreasing the ability or the catalyst to convert the oleflns or naphthenes contained in the charging stock whereas without moisture, the catalyst showed signs of loss in activity after only a few' hours operation. The moisture may be introduced into the catalytic zoneby merely injecting waterinto a preheater through which the vaporized charging stock'is passing on its way into the catalytic reactor. The heat in the vapors and in the preheater vaporizes the water which then with the treated hydrocarbons and steam. This will be recovered with the condensed water which may be recycled to the reactor.

While the above are the preferred catalysts, other catalysts which may be used to transform olefin or naphthenes in hydrocarbons mixtures comprise zinc, cadmium and other metal phosphates, hydroxides of alkali and alkaline earth metals such as sodium, potassium, lithium and calcium hydroxides, metal halides such as zinc, aluminum and iron chlorides and bromides. In general, any catalyst which has heretofore been employed for the purpose of polymerizing gaseous hydrocarbons may be used as catalyst in the process of deolefination of hydrocarbons forming the subject matter of my invention.

The temperature at which the catalytic reaction is carried out depends primarily upon the nature of the transformation desired which in turn depends upon the nature of the stock. For example, when converting naphthene hydrocarbons into aromatic hydrocarbons, I have found that the temperature of operation is higher than when converting olefin hydrocarbons to naphthenes or paraflins. Naphthene hydrocarbons may be converted into aromatic hydrocarbons by operating the catalytic process at a temperature preferably between 850? F. and 1000 F. although lower yields of aromatics per pass may be obtained at temperatures as low as 750 F. Temperatures above 1000 F. may be used particularly when the stock does not contain hydrocarbons that .will cause undesirable side reactions such as the cracking of paraiilns to produce olefins. Olefin hydrocarbons are converted to naphthenes and paraflins at temperatures preferably between 700 F. and 850 F.,

using the catalytic process of my invention although temperatures as low as 600 F. may be used with correspondingly lower yields of transformed materials. The olefin hydrocarbons may also be converted directly to predominantly aromatic hydrocarbons with some paramn and naphthene formation by operating the catalytic process at temperatures above 850 F. The paraffin hydrocarbons may be converted to olefins by carrying out the catalytic reaction at temperatures above 900 F.

Thus, when treating hydrocarbon mixtures by the catalytic process of my invention, I may select and control temperatures suited to the stock to be treated and to the product desired. For example, when treating a hydrocarbon mix-- ture consisting predominantly of naphthenes and paraflins, I may catalytically treat this stock at temperatures between 850 and 900 F.

to convert all of the naphthenes into aromatics without appreciably altering the paraffins. When treating a mixture of hydrocarbons consisting predominantly of olefins and naphthenes, I may select a temperature for the reaction of about 750 to convert the olefins into naphthenes and paraflins without substantially changing the naphthenes into aromatics but by operating at temperatures between 850-900 F., I may convert both the olefins and naphthenes into predominantly aromatics with some paraffin formation. Some naphthenes may be unchanged dependin upon the rate of flow of material through the reactor. When treating a mixture of hydrocarbons consisting predominantly of olefins and paraiilns, I may catalytically treat at about 750 F. and obtain transformation of olefins into naphthenes and paraflins without affecting the parailins present in the charge. However, by increasing the temperature of reaction to 850-900 F., the olefins may be transformed directly into aromatics but the parafllns again will be substantially unchanged.

Pressure influences the reaction in that it re- ,duces the time of the reaction and increases the some cases, is detrimental since it reduces the yield of aromatics. However, by increasing the temperature of the reaction, the detrimental effect of pressure may be overcome.

In general, the process of transforming olefins and napthenes is carried out by simply heating and vaporizing the stock to be treated to the desired-reaction temperature, say 800 F., and passing the vapors through the reactor. containing the catalyst and then condensing the products of the reaction. The reactor is preferably an elongated chamber containing the catalyst absorbed on granules of a suitable carrier. The reactor may be placed in either a horizontal, vertical or inclined position. In commercial operations, it may be desirable to provide a plurality of these reactors so that they may be operated alternately in order to provide for the removal and regeneration of the catalyst. If desired, the reactor may be provided with conveyors for containing the catalyst which may be moved through the reactor and out of the zone of reaction where the used catalyst may be reactivated or replaced with fresh catalyst before being introduced into the reactor. The variations of means and method for providing the catalyst in the reaction zone and for regeneration are obvious to those skilled in the art.

recycled through the reactor in cases where the passage of the stock through the reactor does not produce suflicient deoleflnation or desired transformation. Also, the rate of passage ofthe stock through the reactor, in other words, the reacting time, may be varied to give suflicient time for the feed in the reactor in order to obtain the desired reaction. By providing suflicient time in the reactor, the feed stock may be transformed adequately in a single passage through the reactor.

The condensed products of the reaction may then be treated to recover ,purer aromatic hydrocarbons; This may be accomplished by extracting the treated mixture with a solvent that selectively dissolves the aromatic hydrocarbons in the mixture and rejects as a fraction insoluble in the solvent the non-aromatic hydrocarbons such as the paraffin, naphthenic and other non-aromatic hydrocarbons. By allowing the mixture of treated material and solvent to stratify into two layers, the phase of solvent and aromatic fractions carbons are liquid sulfur dioxide, phenol, dichlor-' ethyl ether, furfural and the like.

The extraction of the treated hydrocarbons also extracts any residual olefins along with the aropassed through the catalyst reactor.

sirable motor fuels.

'lytic method to produce aromatic hydrocarbons matics. If desired, the extract containing the olefins may be retreated by the catalytic method to reduce further the olefins contained in the extract. The thus treated product may be re-extracted to remove non-aromatic hydrocarbons which may have been produced by the retreatment. This'procedure of catalytic treatment and extraction may be repeated as many times as is necessary to produce an extract that issubstantially free from olefins.

If desired, the original stock containing a mix-' ture of hydrocarbons may be first extracted to separate and eoncentrate the olefins and aromatics present in the mixture and the extract may then be treated by the catalytic process to convert the olefins into non-olefinic materials. This, of course; will reduce the amount of stock to be If desired, the product obtained from the reaction may be treated with sulfuric acid to remove any traces of unconverted olefins.

While I have described above a-particularly desirable use of my invention as applied to the purification of aromatic hydrocarbons to remove undesirable olefins, the process may be applied for the production of olefin-free, gum stable motor fuels of high anti-knock which maybe used either per se or as a blend for other gasolines. For example, I may subject apressure distillate composed chiefly of aromatics, parafilns and olefins to the above treatment and produce a motor fuel composed of aromatics, parafllns and naphthenes which is substantially free of olefins and which is posed chiefly of'naphthenes and having a knock rating, for example, of about 75-85 (A. S. T. M.

motor method). By adding a small amount of tetra ethyl lead to this fraction, for example, 3 ml. per gallon of the gasoline, an aviation gasoline of'90-100 knock rating may be produced; The normally liquid oleflns to be processed may be produced by polymerization of normally gaseous olefins.

It is thus another object of my invention to convert olefins into naphthenes to protluce de- As stated above, the catalytic treatment of olefins converts-these hydrocarbons into naphthenes which are at least partially converted into aromatic hydrocarbons. This is particularly true when using a catalyst of phosphoric. acid which has been partially neutralized on the carrier with caustic soda. Instead of treating olefins to produce aromatic hydrocarbons, I may treat naph-* thene hydrocarbons by the above described catawhich may be extracted if desired to produce arog5 matic solvents.

I have also discovered that a motorfuel of suitable boiling range containing naphthene hydrocarbons may be catalytically treated as above to produce a motor fuel of improved anti-knock"fj value. In this treatment, the naphthene hydro- -carbonsare converted into aromatic hydrocarbons which are of higher knock rating than the corresponding naphthenes. The presence of olefins in the charging. stock is notessential as 19118 7| as the gasoline contains naphthene hydrocarbons.

For example, I may catalytically treat a gasoline operated on straight naphthenes, i. e. containing little or materially no other hydrocarbons or the treatment may be carried out on a mixtureof naphthenes and aromatic or paramnic or other hydrocarbons. thene fraction, for example, one containing cyclohexane, methyl cyclopentane, cycloheptane and substituted cyclo paramn and having, for example, an anti-knock value of about 65, I may convert by the above catalytic treatment this fraction into one having a blending anti-knock value of about and above which may be blended with-gasolines of lower anti-knock values.

As stated above. the transformation of olefins to naphthenes and parafiins takes place at lower temperatures than the transformation of naphthenes to aromatics; I have discovered that diefins may be converted to aromatics by carrying the process in several stages of operation in which the temperature in each stage is controlled such that the oleflns are first converted into naphthenes and parafflns in the first stage and the thus produced naphthenes are converted in the second v stageintoaromatics. Thus, by employing temperatures of 700-850 F. in the first stage, the olefins may be converted into naphthenes and parafilns and by employing temperatures above 850 F, in the second stage, the naphthenes may be converted into aromatics. The same type catalyst may be employed in each stage. While as shown previously, the olefins may be converted directly into aromatic in a single stage by operating at temperatures above 850 F., the two stage process has the advantage oi. less loss of material due to formation of gases as this process is carried out at lower temperatures. When treating stocks that are predominantly naphthenes and parafiins containing little or no olefins and it is desired tc obtain the maximum production of aromatics from this stock, the first stage may be operated at higher temperature, 1. e. above 900 F. This high temperature first stage operation will convert the naphthenes into aromatics and will convert the pa'raflins into olefins. The products of the first stage may then be passed through a second stage maintained at a lower temperature, 'i. e., 850-9Q0 F. in order to obtain transformation of the olefins formed in the first reaction zone into aromatics. By recycling a part of the products from the second stage, a product .may eventually be produced consisting of any This may be accomplished first by converting p'aramns to'olefin's" in the first stage andconverting the volefins to aromatics in the second stage and recycling a part ofthese products to obtain a product of any desired aromatic-content.

In the aforementioned two-stage'operation, the charging stock may be either normally liquid or iiormallyi gaseous olefins and/orparafllns to produce the normally liquid' aromatics, parafllns,

naphthenes and olefins. The two-stage catalytic process which is included within the scope of my invention is particularly suited for the reforming of low anti- When treating a straight naphknock gasolines to produc high anti-knock gasolines. Thus, I may'subject gasoline containin appreciable quantities of naphthenes and low knock rating paraflins to the catalytic treatment in the first stage operated at a relatively high temperature, i. e.v above 900 F. to transform paraflln hydrocarbons ,into olefins and naphthenes into aromatics. The products of the first reaction stage may then be passed through a catalytic zone maintained at a lower temperature, i. e. 850-900 F. to transform the olefins into aromatics.

Other objects, features and advantages of my invention will become apparent to those skilled in the art from the following specific examples:

Example 1 A cracked gasolinewas' topped to produce a bottoms fraction having a boiling range of 200 450 F. and containing about 29.2% by weight of olefins. These bottoms were vaporized and the vapors were passed through a reactor consisting of an elongated stainless'steel tube about 4 feet long and about one inch in diameter which contained about 230 ml. of catalyst composed of phosphoric acid adsorbed on charcoal. The

topped gasoline was passed through the reactor at a rate of about 125 ml. per hr. The temperature was maintained in the reactor at about 800 F. Atmospheric pressure was maintained throughout the operation. Water at a rate of 30 ml. per hour was pumped into the vaporized stream of charging stock passing to the reactor. The hydrocarbon vapors and steam passing through the reactor were condensed and the water was removed from the hydrocarbons. The condensate of hydrocarbons was again topped to remove fractions having a boiling point below 200 F. The catalyst was prepared by saturating charcoal particles capable of passing through a screen of 6 mesh and being held on a 14 mesh screen, with 85% phosphoric acid and allowing the excess acid to drain from the the reactor was again topped to 200 F. initial boiling point. A test on the bottoms showed a reduction in olefin to approximately 6.5%. The sulfur content of this product was reduced from 0.68% by weight contained in the original untreated material to 0.13%. The catalyst was further used to treat original feed for approximately 40 additional hours and the tests on the products passing through the reactor still showed a reduction .01 about 50% of olefins per cycle of charging stock.

Example 2 A hydrocarbonfraction having a boiling range of 170-400" F. and composed of 60% by volume of aromatic hydrocarbons consisting chiefly of benzene, toluene and xylene, 14% by volume of olefins. and 26% by volume of paraflins and other non-aromaticand non-olc-finic hydrocarbons was treated withcatalyst at 800 F. as in Example 1. After the first cycle of operation. the product of reaction showed an olefin content of 5.6%. This was reduced to 3.2% by recycling the once treated product through the reactor containing the catalyst under the, same conditions of-operaticn.

The liquid products of the reaction were then mixed with 2 volumes of liquid sulfur dioxide at a temperature of about -l8- F. and the mixture was allowed to stratify into two layers consisting of an upper layer of non-aromatic hydrocarbons dissolved in a small amount of the sulfur dioxide and a lower layer consisting of the aromatic hydrocarbons dissolved in the bulk of the liquid sulfur dioxide. The lower layer was withdrawn and the liquid sulfur dioxide was distilled to produce a fraction of aromatic hydrocarbons and representing about 65% by volume of the material undergoing extraction. The extracted aromatics contained the small amount of unconverted olefins which were present in the treated stock and which were extracted along with the aromatics.

Example 3 A pressure distillate was topped, to produce a hydrocarbon fraction having a boiling range of 196 -410 F. and composed of 20% olefins, 15% aromatics, 48% naphthenes and 17% parafiins.

ring until dry without added heat. Then 25 ml.

of 20% aqueous sodium hydroxide was added to the charcoal containing the phosphoric acid and the mixture was stirred well. while drying with the application of gentle heat. The amount ofcaustic soda added to the charcoal containing the phosphoric acid represented one-half equivalent of the alkali per mol of the acid. The

total product recovered at the end of five hours of operation from the reactor which represented 93% of the feed charged to the reactor consisted of a hydrocarbon fraction having a boiling range of -429 F.'and consistedlof 2% olefins, 37%

naphthenes, 26% aromatics and about 35% parafiins which was obtained in a single pass through the reactor. Very little gas was produced during the treatment and this consisted of 58.4% hydrogen, 1.4% olefins, 35.6% parafflns and 4.6% of material soluble in caustic soda.

The above treatment was repeated using the same feed stock, temperatures. pressure and catalysts in which the phosphoric acidadsorbed on the charcoal-was partially neutralized by various equivalents of caustic soda per mol of the phosphoric acid. Thefollowing table contains a summary of the catalyst used and the composition of the resulting product together with the gravity and" Engler distillation of the final product. Included also are tests on the feed stock which was subjected to the treatment,

The product obtained by the treatment stock with phosphoric acid neutralized with onehalf equivalent of caustic soda per mol of acid and having. a composition of 2% olefins, 26% aromatics, 37% naphthenes and 35%paraiins was retreated using the same catalyst but at a higher temperature, i. e. 850-900 F. The resulting product which represented about 94% of the once treated feed stock showed an aromatic content of 65%, a paramn content of 33% and an of the v olefin content of 2% indicating man of the naphthenes were converted into aromatics.

Example I Apolymergasolinehavingaboilingrangeoi 5 80-890 1". and composed of appoxlmately 80% oleflns and paramnswastreatedinacoordance with Example 8 using the phosphoric acid catalyst which had been neutralised with onehali equivalent of causticsodaper moi of acid. 1

lowed by neutralizing said phosphoric acid on said carrier with approximately one-sixth to two-thirds equivalents of ac'austic alkali per mol oi said acid.

2. A process for converting hydrocarbons 4 which comprises heating said hydrocarbonsto a temperature of the order oi 600 to 1000' I". for a sumcient period oitime to convert said hydrocarbons, in the presence of a ca alyst Prepared by adsorbing phosphoric acid on carbon followed by neutralizing said phosphoric acid on said carbon with approximately one-sixth to two-thirds equivalents of a caustic alkali per mol of said acid.

15 3. A' process for converting hydrocarbons Ten: 1

. Compositiondtrestsdproduot, mum Gm Engierdistiliatlom'l'. Catalyst used: NICK permol 0! A. 1% HsPOmnclmeosi e Oleiias m a man 1 m or ice thence om 0% v 1 no mo m 48.0 no '211 an an 420 2.4 n4 an an 41.5 use no see m 422 2.4 no sea no 41.4 no no mo v1m no so no no no 41.0 m1 and m no as no voao 34.1 41.1 111 an m an ac 4.5 21.0 an 34.0 41.8 .112 as no 4 :11 4:1 1 5.2 an 41.5 33.0 41.1 111 no an :11 4a m 5.0 21.0 41.0 sac 41.1; 111 an no s1: 4:1 8.1 10.0 45.0 21.0 no 182 as so 315 4:0 se ui is: 11.0 40.0 ass as: 185 no m. 314 m Omnpcsltion and tests on iced 1 I 1 stock. no 15.0 4ao 11.0 48.5 no as a, on 410 lmpleS whichcomprisesheating'said hydrocarbonsto' a straightrungasoline was extracted-with :2-

volumes or liquidsulrurdioxick at is I". to produeeanextractconsistingor50%aromatics,$0%

- n'aphthenesandzflfiiparamns. 'lhisrractionwas M08117 treated 81; 850-900 1'. Elm- 4o phericpressureasinExample3,usingthephos- 'phoric acid catalyst neutralized-with one-halt equivalentoicausticsodapermoloitheacid.

The treated produotflobtained in as llslopess throughthereactorandrepresenting aboutflfi byvolumeortheteedstockintroducedintothe reactor consisted of 80% aromatics and 20% paramns. Thegravityandlmgierdistillationo! .theextract'reedstockandtheflnalproductare givenbelow:

-. 1m mum's.

or I a oo' nnmu 10% 1m 00% 05% Max.

G-oline ex 41 m 241 as: no so: Iss2 l'inslprodnct.- 31 m 2:: 411 an as as m ioregoingdescriptionis notto-be ma my invention but merely as illustrative a temperature'oi'the order or 600 to 1000 I". foo-asuilicientperiodortimetoconvertsaidhydrocarbonainthepresenceolacatalystpreparedbyadsorbingphosphoricacidonanacti- 'vated carbon iollowedbyneutraiislngsaidphosphoric acid 'on said activated carbon with approximatelyone-slxth to two-thirds equivalents otacausticalkalipermoloisaldacid.

4.1L process for the production of aromatic hydrocarbonsfromnon-aromatic whichcomprisesheatingsaid toa temperatureot the order of $00 to mp0 I. fora of timeto dehvdmgenate and cyclicise said hy-' drocarbons,inthepreseneeoiacatalystprefollowed by neutralising said phosphoric acldcm.

said carrier with, approximately oione'modeoicarryingitoutasmanyvariations BftWWWI-d, M cum, M w

maybe made thereon as'willberecogni'sedby thoseskilledintheartwhicharewithinthe-scope otthet oliowingclaims.

Iclaim:

1. A rocess f r converting hydrocarbons 10 which comprises heating saidhydrocarbons to -a temperature of the'o'rder- 01 800 to 1000' 1 .101- av suihcient period of time to convert said hydrocarbons, in the presence or acatalyst mp1 oi-said acid.

6.aproeessi'ortheproductionoraromatic .i'rom nonwhich comprises heating saidhydrocarbcns to a temperature of the. order of 600 to 1000' I".

'forasuflioientperiodoi'timetodehydmlm and cyelicis'e said hydrocarbons, in the presence of a catalyst preparedby adsorbingi m acid oncarbon iollowed by neutralising said by ed i t phosphoric acidon a 101- I8 phosphoric acid on g with nub mately one-sixth to two-thirds equivalents of a caustic alkali per mol of said acid.

1. A process for the production of aromatic hydrocarbons from non-aromatic hydrocarbons which comprises heating said hydrocarbons to a temperature of the order of 600 to :1000" F. for a sufficient period of time to dehydrogenate and cyclicize said hydrocarbons, in the presence of a catalyst prepared by adsorbing phosphoric acid on an activated carbon followed by neutralizing said phosphoric acid on said activated carbon with approximately one-sixth to twothirds equivalents of a caustic alkali per mol of said acid.

8. A process for the production of aromatic hydrocarbons boiling in the gasoline range from naphthene hydrocarbons boiling in the gasoline range which comprises'heating said hydrocarbons to a temperature of the order of 600 to 1000 F. for a sufiicient periodof time to dehydrogenate and cyclicize said hydrocarbons, in the presenceof a catalyst prepared by adsorbing phosphoric acid on a carrier followed by neutralizing proximately one-sixth to two-thirds equivalents of a caustic alkali per mol of said acid.

9. A process according to claim 8,, in which said carrier is carbon.

10. A process according to claim 8, in which said carrier is an activated carbon and said heating temperature is approximately 850-1000 F.

- said phosphoric acid on said carrier with ap- 11. A process forthe production of aromatic hydrocarbons boiling in the gasoline range from olefin hydrocarbons boiling in the gasoline range which comprises heating said hydrocarbons to a temperature of the order of 600 to 1000 F. for a suflicient period of time to dehydrogenate and cyclicize said hydrocarbons, in the presence of a catalyst prepared by adsorbing phosphoric acid on a carrier followed by neutralizing said phosphoric acid on said carrier with approximately one-sixth to two-thirds equivalent-s of a caustic alkali per mol of said acid.

12. A process according to claim 11, in which said carrier is carbon.

13. A process according to claim 11, in which said carrier is an activated carbon and said heating temperature is approximately 750-850 F.

14. A process for converting paraflin hydro-- carbons which comprises heating said hydrocarbons to a temperature of the order of 600 to 1000 F. for a suflicient period of time to convert said hydrocarbons, in the presence of a catalyst prepared by adsorbing phosphoric acid on a carrier followed by neutralizing said phos phoric acid on said carrier with approximately one-sixth to two-thirds equivalents of a caustic alkali per mol of said acid.

15. A process according to claim 5, in which said carrier is an activated charcoal.

KARL KORPI. 

